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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Kinetics and products of the reactions of OH radicals with cyclohexene, 1-methyl-1-cyclohexene, cis -cyclooctene, and cis -cyclodecene
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Kinetics and products of the reactions of OH radicals with cyclohexene, 1-methyl-1-cyclohexene, cis -cyclooctene, and cis -cyclodecene

机译：OH自由基与环己烯，1-甲基-1-环己烯，顺式-环辛烯和顺式-环癸烯的反应动力学和产物

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Rate constants for the reactions of OH radicals with four C _6-C _(10) cycloalkenes have been measured at 297 ± 2 K using a relative rate technique. The rate constants (in units of 10 ~(-11) cm ~3 molecule ~(-1) s ~(-1)) were cyclohexene, 6.35 ± 0.12; cis-cyclooctene, 5.16 ± 0.15; cis-cyclodecene, 4.18 ± 0.06; and 1-methyl-1-cyclohexene, 9.81 ± 0.18, where the indicated errors are two least-squares standard deviations and do not include uncertainties in the rate constant for the reference compound 1,3,5-trimethylbenzene. In addition, a rate constant of (4.8 ± 1.3) × 10 ~(-11) cm ~3 molecule ~(-1) s ~(-1) was derived for the reaction of OH radicals with 1,6-hexanedial, relative to our measured rate constant for OH + cyclohexene. Analyses of products of the OH + cyclohexene, 1-methyl-1-cyclohexene, and cis-cyclooctene reactions by direct air sampling atmospheric pressure ionization mass spectrometry and/or by combined gas chromatography-mass spectrometry showed the presence of products attributed to cyclic 1,2-hydroxynitrates and the dicarbonyls 1,6-hexanedial, 6-oxo-heptanal, and 1,8-octanedial, respectively. These dicarbonyl products, which are those formed after decomposition of the intermediate cyclic 1,2-hydroxyalkoxy radicals, were quantified as their dioximes, with molar formation yields of 76 ± 10%, 82 ± 12%, and 84 ± 18% from the cyclohexene, 1-methyl-1-cyclohexene, and cis-cyclooctene reactions, respectively. Combined with literature data concerning 1,2-hydroxynitrate formation from OH + alkenes and the estimated fractions of the overall reactions proceeding by H-atom abstraction, 90 ± 12%, 95 ± 13% and 108 ± 20% of the products or reaction pathways from the OH radical-initiated reactions of cyclohexene, 1-methyl-1-cyclohexene, and cis-cyclooctene in the presence of NO are accounted for.
机译：已使用相对速率技术在297±2 K下测量了OH自由基与四种C 6-C _（10）环烯烃反应的速率常数。速率常数（以10〜（-11）cm〜3分子〜（-1）s〜（-1）为单位）为环己烯，6.35±0.12;顺式环辛烯，5.16±0.15;顺式环癸烯，4.18±0.06; 1-甲基-1-环己烯为9.81±0.18，其中所示误差为两个最小二乘法标准偏差，并且不包括参考化合物1,3,5-三甲基苯的速率常数的不确定性。此外，对于OH基与1,6-己二醛的相对反应，得出了（4.8±1.3）×10〜（-11）cm〜3分子〜（-1）s〜（-1）的速率常数。达到我们对OH +环己烯测得的速率常数。通过直接空气采样大气压电离质谱和/或通过气相色谱-质谱联用分析OH +环己烯，1-甲基-1-环己烯和顺式环辛烯反应的产物，结果表明存在归因于环1的产物，2-羟基硝酸盐和二羰基的1，6-己二醛，6-氧杂庚醛和1，8-辛二醛。这些二羰基产物是在中间体环状1,2-羟基烷氧基分解后形成的，被定量为其二肟，从环己烯的摩尔形成产率分别为76±10％，82±12％和84±18％。 ，1-甲基-1-环己烯和顺式环辛烯反应。结合有关由OH +烯烃形成1,2-羟基硝酸盐的文献数据以及通过H原子抽象进行的总体反应的估计馏分，生成产物或反应途径的90±12％，95±13％和108±20％解释了在NO存在下环己烯，1-甲基-1-环己烯和顺式环辛烯的OH自由基引发的反应。

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